Substituted aryl keto-enolic heterocycles

ABSTRACT

The aryl-keto-enolic heterocycles according to the invention have the formula (I), in which Het stands for a heterocyclic group from the series (a), (b) or (c), and X, Y, Z, n, A, B, E, L and M have the meanings given in the description. The compounds having the formula (I) are pesticides, in particular acaricides, insecticides, fungicides and herbicides. Also disclosed is their preparation. ##STR1##

This is a filing under 35 U.S.C. § 371 of PCT/EP94/02042, filed Jun. 22,1994.

The present invention relates to novel substituted aryl keto-enolicheterocycles, to a number of processes for their preparation and totheir use as pesticides.

It is known that certain substituted Δ³ -dihydrofuran-2-one derivativespossess herbicidal properties (cf. DE-A 4 014 420). The synthesis of thetetronic acid derivatives (such as for example3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)Δ³ -dihydrofuran-2-one)used as starting compounds is likewise described in DE-A 4 014 420.Compounds of similar structure, without the indication of insecticidaland/or acaricidal activity, are known from the publication Campbell etal., I. Chem. Soc., Perkin Trans. 1 1985, (8) 1567-76.

Pharmaceutical properties have been described previously for3-acyl-pyrrolidine-2,4-diones (S. Suzuki et al. Chem. Pharm. Bull. 151120 (1967)). Furthermore, N-phenyl-pyrrolidine-2,4-diones have beensynthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 19851095). A biological activity of these compounds has not been described.

EP-A 0 262 399 discloses compounds of similar structure(3-aryl-pyrrolidine-2,4-diones) for which, however, no herbicidal,insecticidal or acaricidal action has become known. Known to have aherbicidal, insecticidal or acaricidal action are unsubstituted,bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A 355 599 and EP415 211), substituted bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP 501 129) and substituted mono-cyclic 3-aryl-pyrrolidine-2,4-dionederivatives (EP-A 377 893, EP 442 077 and EP 497 127).

Polycyclic 3-aryl-pyrrolidine-2,4-dione derivatives (EP-A442 073),1H-3-aryl-pyrrolidine-dione derivatives (EP 456 063 and EP 521 334) andsubstituted bicyclic 3-aryl-pyrrolidine-dione derivatives (EP 501 129)are also known.

Also known are tetronic acid derivatives having fungicidal, herbicidal,acaricidal and insecticidal properties (EP 528 156).4-Arylpyrazolidine-dione derivatives having herbicidal, acaricidal andinsecticidal properties are described in WO 92/16510 and EP 508 126.

Novel substituted aryl keto-enolic heterocycles have now been found ofthe formula (I) ##STR2## in which X represents alkyl, halogen or alkoxy,

Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl,

Z represents alkyl, halogen or alkoxy,

n represents a number 0, 1, 2 or 3,

Het represents a heterocyclic group from the series ##STR3## A and B canbe identical or different and represent hydrogen, in each caseoptionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,alkylthioalkyl, cycloalkyl which is optionally interrupted by at leastone heteroatom, or aryl, aralkyl or hetaryl each of which is optionallysubstituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy ornitro,

or in which

A and B, together with the carbon atom to which they are attached, forma saturated or unsaturated ring which is optionally interrupted by atleast one heteroatom and is optionally substituted,

E represents hydrogen, in each case optionally halogen-substitutedalkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl which isoptionally interrupted by at least one heteroatom, or aryl, aralkyl orhetaryl each of which is optionally substituted by halogen, alkyl,halogenoalkyl, alkoxy, halogenoalkoxy or nitro,

or in which

A and E, together with the atoms to which they are attached, form asaturated or unsaturated monocyclic, bicyclic or tricyclic ring systemwhich is optionally interrupted by at least one heteroatom and isoptionally substituted,

L represents an alkanediyl group,

M represents one of the following groups: ##STR4## in which R¹represents hydrogen or alkyl,

R² represents in each case optionally substituted alkyl, alkenyl,alkinyl, cycloalkyl, alkoxyalkyl, alkylthioalkyl, aryl or aralkyl,

R³ represents optionally substituted alkyl, aryl or aralkyl,

R⁴ represents hydrogen, halogen, in each case optionally substitutedalkyl or phenyl,

R⁵ represents hydrogen, halogen or optionally substituted alkyl,

Q represents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, CNor nitro, and

m represents a number 0, 1, 2 or 3,

and the enantiomerically pure forms of compounds of the formula (I).

Depending on the substituents, the compounds of the formula (I) can bepresent as geometrical and/or optical isomers or isomer mixtures ofvarying compositions. Both the pure isomers and the isomer mixtures, thepreparation and use thereof, and compositions comprising them are partof the claimed invention. However, for the sake of simplicity the textbelow refers always to compounds of the formula (I) although what ismeant are both the pure compounds and, if appropriate, mixtures withvarying proportions of isomeric compounds.

It has also been found that the novel compounds of the formula (I) havea very good activity as pesticides, preferably as arthropodicides,fungicides and herbicides.

It additionally been found that the novel substituted aryl keto-enolicheterocycles of the formula (Ia) ##STR5## in which A, B, L, M, X, Y, Zand n have the meaning given above are obtained if

(A) Compounds of the formula (IIa) ##STR6## in which A, B, X, Y, Z and nhave the meaning given above are reacted with compounds of the formula(III)

    G--L--M                                                    (III)

in which

L and M have the meaning given above

and

G represents a leaving group, such as halogen, sulphonylalkyl orsulphonylaryl in the presence of a diluent and in the presence of abase.

(B) in addition, compounds of the formula (Ib) ##STR7## in which A, B,E, L, M, X, Y, Z and n have the meaning given above are obtained ifcompounds of the formula (IIb) ##STR8## in which A, B, E, X, Y, Z and nhave the meaning given above are reacted with compounds of the formula(III)

    G--L--M                                                    (III)

in which

L and M have the meaning given above

and

G represents a leaving group, such as halogen, sulphonylalkyl orsulphonylaryl,

in the presence of a diluent and in the presence of a base.

(c) Moreover, compounds of the formula (Ic) ##STR9## in which A, E, L,M, X, Y, Z and n have the meaning given above are obtained if compoundsof the formula (IIc) ##STR10## in which B, E, X, Y, Z and n have themeaning given above are reacted with compounds of the formula (III)

    G--L--M                                                    (Ill)

in which

L and M have the meaning given above

and

G represents a leaving group, such as halogen, sulphonylalkyl orsulphonylaryl, in the presence of a diluent and in the presence of abase.

Surprisingly, the novel substituted aryl keto-enolic heterocycles (Ia),(Ib) and (Ic) display good acaricidal, insecticidal and herbicidalproperties.

The compounds according to the invention are defined in general by theformula (I).

X preferably represents C₁ -C₆ -alkyl, halogen or C₁ -C₆ -alkoxy.

Y preferably represents hydrogen, C₁ -C₆ -alkyl, halogen C₁ -C₆ -alkoxyor C₁ -C₃ -halogenoalkyl.

Z preferably represents C₁ -C₆ -alkyl, halogen or C₁ -C₆ -alkoxy.

n preferably represents a number from 0 to 3.

Het preferably represents a heterocyclic group from the series ##STR11##in which A and B are identical or different and represent hydrogen or ineach case optionally halogen-substituted straight-chain or branched C₁-C₁₂ -alkyl, C₃ -C₈ -alkenyl, C₁ -C₁₀ -alkoxy-C₂ -C₈ -alkyl, C₁ -C₈-polyalkoxy-C₂ -C₈ -alkyl, C₁ -C₁₀ -alkylthio-C₂ -C₈ -alkyl, cycloalkylhaving 3 to 8 ring atoms, which can be interrupted by oxygen and/orsulphur, or phenyl, pyrimidyl, imidazolyl, pyrazolyl, triazolyl,indolyl, thiazolyl or phenyl-C₁ -C₆ -alkyl each of which is optionallysubstituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆-alkoxy, C₁ -C₆ -halogenoalkoxy or nitro,

or in which

A and B, together with the carbon atom to which they are attached, forma saturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byhalogen, C₁ -C₆ -alkyl, C₁ -C₆ alkoxy, C₁ -C₄ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, C₁ -C₄ -alkylthio or phenyl which is optionallysubstituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy,

E represents hydrogen or in each case optionally halogen-substitutedstraight-chain or branched C₁ -C₁₂ -alkyl, C₃ -C₈ -alkenyl, C₁ -C₁₀-alkoxy-C₂ -C₈ -alkyl, C₁ -C₈ -polyalkoxy-C₂ -C₈ -alkyl, C₁ -C₁₀-alkylthio-C₂ -C₈ -alkyl, cycloalkyl having 3 to 8 ring atoms, which canbe interrupted by oxygen and/or sulphur, or phenyl, pyrimidyl,imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁ -C₆-alkyl each of which is optionally substituted by halogen, C₁ -C₆-alkyl, C₁ -C₆ -haloalkyl, C₁ -C₆ -alkoxy, C₁ -C₆ -halogenoalkoxy ornitro,

or in which

A and E, together with the atoms to which they are attached, form asaturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byhalogen, C₁ -C₆ -alkyl, C₁ -C₆ alkoxy, C₁ -C₄ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, C₁ -C₄ -alkylthio or phenyl which is optionallysubstituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy,

or, if Het in formula (I) represents a pyrazolinone ring,

A and E, together with the two nitrogen atoms of the pyrazoline ring,represent a group of the formulae 1 to 4 listed below ##STR12## which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents consisting of C₁ -C₆ -alkyl, C₁ -C₆ -halogenoalkyl orhalogen.

L preferably represents an alkanediyl group having 1 to 6 carbon atoms.

M preferably represents one of the following: ##STR13## R¹ preferablyrepresents hydrogen or C₁ -C₁₂ -alkyl. R² preferably represents in eachcase optionally halogen-substituted C₁ -C₁₂ -alkyl, C₃ -C₈ -alkenyl, C₃-C₈ -alkinyl, C₃ -C₈ -cycloalkyl, C₁ -C₈ -alkoxy-C₂ -C₈ -alkyl, C₁ -C₈-alkylthio-C₂ -C₈ -alkyl or phenyl or benzyl each of which is optionallysubstituted by halogen, nitro, cyano, C₁ -C₆ -alkoxy, C₁ -C₆ haloalkoxy,C₁ -C₆ -alkylthio, C₁ -C₆ -haloakylthio, C₁ -C₆ -alkyl or C₁ -C₆-halogenoalkyl.

R³ preferably represents optionally halogen-substituted C₁ -C₁₂ -alkyl,or represents phenyl or benzyl each of which is substituted by halogen,C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy.

R⁴ preferably represents hydrogen, halogen, optionallyhalogen-substituted C₁ -C₆ -alkyl or phenyl which is in each casesubstituted by halogen, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, cyano or nitro.

R⁵ preferably represents hydrogen, halogen or optionallyhalogen-substituted C₁ -C₆ -alkyl.

Q preferably represents halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy, cyano or nitro.

m preferably represents a number 0, 1, 2 or 3.

X particularly preferably represents C₁ -C₆ -alkyl, fluorine, chlorine,bromine or C₁ -C₆ -alkoxy.

Y particularly preferably represents hydrogen, C₁ -C₆ -alkyl, fluorine,chlorine, bromine, C₁ -C₆ -alkoxy or C₁ -C₂ -halogenoalkyl.

Z particularly preferably represents C₁ -C₄ -alkyl, fluorine, chlorine,bromine or C₁ -C₄ -alkoxy.

n particularly preferably represents a number from 0 to 2.

Het particularly preferably represents a heterocyclic group from theseries ##STR14## in which A and B are identical or different andrepresent hydrogen, in each case optionally halogen-substitutedstraight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆ -alkenyl, C₁ -C₈-alkoxy-C₂ -C₆ -alkyl, C₁ -C₆ -polyalkoxy-C₂ -C₆ -alkyl, C₁ -C₈-alkylthio-C₂ -C₆ -alkyl, cycloalkyl having 3 to 7 ring atoms, which canbe interrupted by 1-2 oxygen and/or sulphur atoms, or phenyl, pyridinyl,imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁ -C₄-alkyl each of which is optionally substituted by halogen, C₁ -C₄-alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, or nitro,

or in which

A and B, together with the carbon atom to which they are attached, forma saturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byhalogen, C₁ -C₅ -alkyl, C₁ -C₅ alkoxy, C₁ -C₃ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, C₁ -C₃ -alkylthio or phenyl which is optionallysubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,

E represents hydrogen or in each case optionally halogen-substitutedstraight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆ -alkenyl, C₁ -C₈-alkoxy-C₂ -C₆ -alkyl, C₁ -C₆ -polyalkoxy-C₂ -C₆ -alkyl, C₁ -C₈-alkylthio-C₂ -C₆ -alkyl, cycloalkyl having 3 to 7 ring atoms, which canbe interrupted by 1-2 oxygen and/or sulphur atoms, or phenyl, pyridinyl,imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl or phenyl-C₁ -C₄-alkyl each of which is optionally substituted by halogen, C₁ -C₄-alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₄ -alkoxy or nitro,

or in which

A and E, together with the atoms to which they are attached, form asaturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byhalogen, C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, C₁ -C₃ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, C₁ -C₃ -alkylthio or phenyl which is optionallysubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,

or, if Het in formula (I) represents a pyrazolinone ring,

A and E, together with the two nitrogen atoms of the pyrazoline ring,represent a group of the formulae 1 or 2 listed below which isoptionally monosubstituted or polysubstituted by identical or differentsubstituents consisting of C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl,fluorine or chlorine, ##STR15## L particularly preferably represents analkanediyl group having 1 to 4 carbon atoms.

M particularly preferably represents one of the following groups:##STR16## R¹ particularly preferably represents hydrogen or C₁ -C₁₀-alkyl.

R² particularly preferably represents in each case optionally fluorine-,chlorine-, bromine-substituted C₁ -C₁₀ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆-alkinyl, C₃ -C₈ -cycloalkyl, C₁ -C₆ -alkoxy-C₂ -C₆ -alkyl, C₁ -C₆-alkylthio-C₂ -C₆ -alkyl, or phenyl or benzyl each of which isoptionally substituted by fluorine, chlorine, bromine, nitro, cyano, C₁-C₄ -alkylthio, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄-halogenoalkylthio, C₁ -C₄ -alkyl or C₁ -C₄ -halogenoalkyl.

R³ particularly preferably represents optionally fluorine-, chlorine-,bromine-substituted C₁ -C₁₀ -alkyl, or represents phenyl or benzyl eachof which is substituted by fluorine, chlorine, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy.

R⁴ particularly preferably represents hydrogen, fluorine, chlorine,bromine, optionally fluorine- or chlorine-substituted C₁ -C₅ -alkyl orphenyl which is substituted by fluorine, chlorine, bromine, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkyl, C₁ -C₂ -haloalkoxy, cyanoor nitro.

R⁵ particularly preferably represents hydrogen, fluorine, chlorine,bromine or optionally fluorine- or chlorine-substituted C₁ -C₄ -alkyl.

Q particularly preferably represents fluorine, chlorine, bromine, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -haloalkyl, C₁ -C₂ -haloalkoxy, cyano ornitro.

m particularly preferably represents a number 0, 1, or 2.

X very particularly preferably represents methyl, ethyl, propyl,isopropyl, fluorine, chlorine, bromine or methoxy.

Y very particularly preferably represents hydrogen, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, tert-butyl, fluorine, chlorine,bromine, methoxy, ethoxy and trifluoromethyl.

Z very particularly preferably represents methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, fluorine, chlorine, bromine,methoxy and ethoxy.

n very particularly preferably represents 1.

Het very particularly preferably represents a heterocyclic group fromthe series ##STR17## in which A and B are identical or different andrepresent hydrogen, in each case optionally fluorine- orchlorine-substituted straight-chain or branched C₁ -C₈ -alkyl, C₃ -C₄-alkenyl, C₁ -C₆ -alkoxy-C₂ -C₄ -alkyl, C₁ -C₄ -polyalkoxy-C₂ -C₄-alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, cycloalkyl having 3 to 6 ringatoms, which can be interrupted by 1-2 oxygen and/or sulphur atoms, orphenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁ -C₃ -alkyl each ofwhich is optionally substituted by fluorine, chlorine, methyl, ethyl,propyl isopropyl, methoxy, ethoxy, trifluoromethyl or nitro,

or in which

A and B, together with the carbon atom to which they are attached, forma saturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byfluorine, chlorine, C₁ -C₄ -alkyl, C₁ -C₄ alkoxy, trifluoromethyl, C₁-C₂ -alkylthio or phenyl which is optionally substituted by fluorine,chlorine, methyl, methoxy,

E represents hydrogen or in each case optionally fluorine- orchlorine-substituted straight-chain or branched C₁ -C₈ -alkyl, C₃ -C₄-alkenyl, C_(l) -C₆ -alkoxy-C₂ -C₄ -alkyl, C₁ -C₄ -polyalkoxy-C₂ -C₄-alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, cycloalkyl having 3 to 6 ringatoms, which can be interrupted by 1-2 oxygen and/or sulphur atoms, orrepresents phenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁ -C₃-alkyl which is optionally substituted by fluorine, chlorine, methyl,ethyl, propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro,

or in which

A and E, together with the atoms to which they are attached, form asaturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byfluorine, chlorine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl, C₁-C₂ -alkylthio or phenyl which is optionally substituted by fluorine,chlorine, methyl, methoxy,

or, if Het in formula (I) represents a pyrazolinone ring,

A and E, together with the two nitrogen atoms of the pyrazoline ring,represent a group of the formulae 1 or 2 listed below which isoptionally monosubstituted to trisubstituted by identical or differentsubstituents consisting of methyl, fluorine or chlorine, ##STR18## Lvery particularly preferably represents one of the following groups.##STR19## M very particularly preferably represents one of the followinggroups: ##STR20## R¹ very particularly preferably represents hydrogen orC₁ -C₈ -alkyl.

R² very particularly preferably represents in each case optionallyfluorine-, chlorine-, bromine-substituted C₁ -C₈ -alkyl, C₃ -C₄-alkenyl, C₃ -C₄ -alkinyl, cyclopropyl, cyclopentyl, cyclohexyl, C₁ -C₆-alkoxy-C₂ -C₄ -alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, or representsphenyl or benzyl each of which is optionally substituted by fluorine,chlorine, bromine, nitro, cyano, methylthio, ethylthio, methoxy, ethoxy,trifluoromethylthio, trifluoromethoxy, methyl, ethyl, trifluoromethyl.

R³ very particularly preferably represents in each case optionallyfluorine-, chlorine-, bromine-substituted C₁ -C₈ -alkyl, or phenyl orbenzyl which is substituted by fluorine, chlorine, C₁ -C₂ -alkyl or C₁-C₂ -alkoxy.

R⁴ very particularly preferably represents hydrogen, fluorine, chlorine,optionally fluorine- or chlorine-substituted C₁ -C₄ -alkyl, or phenylwhich is substituted by fluorine, chlorine, methyl, ethyl, methoxy,ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano ornitro.

R⁵ very particularly preferably represents hydrogen, fluorine, chlorineor optionally fluorine- or chlorine-substituted methyl, ethyl, propyl orisopropyl.

Q very particularly preferably represents fluorine, chlorine, methyl,ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy,trifluoromethyl, difluoromethoxy, trifluoromethoxy, cyano or nitro.

m very particularly preferably represents a number from 0 to 2.

In each of these sets of definitions the enantiomerically pure forms ofcompounds of the formula (I) are included.

The above-listed radical definitions and explanations, whether generalor listed in ranges of preference, can be combined with one another asdesired, i.e. including combinations between the respective ranges andranges of preference. They apply to the end products and to theprecursors and intermediates.

Preference is given in according with the invention to the compounds ofthe general formula (I) in which there is a combination of thedefinitions listed above as being preferred (preferably).

Particular preference is given in accordance with the invention to thecompounds of a general formula (I) in which there is a combination ofthe definitions listed above as being particularly preferred.

Very particular preference is given in accordance with the invention tothe compounds of the general formula (I) in which there is a combinationof these definitions listed above as being very particularly preferred.

Using 3-(2,4-dichlorophenyl)-4-hydroxy-5-methyl-Δ³ -furan-2-one andchloromethyl ethyl ether in accordance with process (A), the course ofthe process according to the invention can be illustrated by thefollowing equation: ##STR21##

Using 3-(2,6-dichlorophenyl)-4-hydroxy-1-isopropyl-Δ³ -pyrrolin-2-oneand ethyl N-chloromethyl-N-methyl-carbamate in accordance with process(B), the course of the process according to the invention can beillustrated by the following equation. ##STR22##

Using 3-(2,4,6-trimethylphenyl)-5-hydroxy-1,2-tetramethylene-Δ⁴-pyrazolin-3-one and chloromethyl phenyl ether in accordance withprocess (C), the process according to the invention can be illustratedby the following equation: ##STR23##

The compounds of the formula (IIa) ##STR24## in which A, X, Y, Z and nhave the meaning given above, which are required as starting materialsin the process (A), are known (EP 528 156).

The compounds of the formula (IIb) ##STR25## in which A, B, E, X, Y, Zand n have the meaning given above, which are required as startingmaterials in the process (B), are known (cf. for example, EP 355 999, EP377 893, EP 415 211, EP 442 073, EP 456 063, EP 497 127, EP 501 129).

The compounds of the formula (IIc) ##STR26## in which E, B, X, Y, Z andn have the meaning given above,

which are required as starting materials in the process (C), are known(cf. for example WO 92/16510 and EP 508 126).

The compounds of the formula (III) which are additionally required asstarting compounds for carrying out the processes (A), (B) and (C)according to the invention are generally known compounds of organicchemistry.

Diluents which can be used for carrying out the processes (A), (B) and(C) according to the invention are all solvents which are inert withrespect to these compounds. Preferred possibilities for use arehydrocarbons, such as benzine, benzene, toluene, xylene and tetralin;also halogenated hydrocarbons, such as methylene chloride, chloroform,carbon tetrachloride, chlorobenzene and o-dichlorobenzene; ethers, suchas diethyl ether, tetrahydrofuran and dioxane; nitriles, such asacetonitrile or propionitrile; and also polar solvents which are inertwith respect to the compounds of the formula (III), such as dimethylsulphoxide, dimethylformamide, sulpholane or N-methylpyrrolidone.

Bases which can be employed in carrying out the processes (A), (B) and(C) according to the invention are all customary acid acceptors.Preferred possibilities for use are alkali metal and alkaline earthmetal oxides, hydroxides and carbonates, such as sodium hydroxide,potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate,potassium carbonate and calcium carbonate, which can also be employed inthe presence of phase transfer catalysts such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen464*) or TDA 1***). Alkali metal and alkaline earth metal hydrides, suchas sodium amide, sodium hydride and calcium hydride, and also alkalimetal alcoholates as well, such as sodium methylate, sodium ethylate andpotassium tertbutulate, can also be employed. In addition, tertiaryamines, such as triethylamine, pyridine, DABCO, DBU, DBA, Hunig base andN,N-dimethylaniline.

The reaction temperatures when carrying out the processes (A), (B) and(C) according to the invention can be varied within a relatively widerange. The processes are generally carried out at temperatures ofbetween -20° C. and 180° C., preferably 0° C. and 130° C.

When carrying out the processes (A), (B) and (C) according to theinvention, the reaction components (IIa) and (III) or (IIb) and (III) or(IIc) and (III) and the base are generally employed in approximatelyequimolar quantities. However, it is also possible to use one or othercomponent in a relatively large excess (up to 3 mol).

The processes (A), (B) and (C) according to the invention are generallycarried out under atmospheric pressure. The products are worked up bycustomary methods.

The active compounds are suitable for combating animal pests, preferablyarthropods and nematodes; in particular insects and arachnida,encountered in agriculture, in forestry, in the protection of storedproducts and of materials, and in the hygiene field, and have good planttolerance and they are active against normally sensitive and resistentspecies and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,

Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonycus spp., Tetranychus spp.

The active compounds according to the invention are distinguished by ahigh insecticidal and acaricidal activity.

They can be employed with particular success in combattingphytopathogenic mites, for example against the common spider mite ortwo-spotted spider mite (Tetranychus urticae) or against the fruit treered spider mite (Panonychus ulmi).

The active compounds according to the invention additionally display afungicidal activity, an activity against Pyricularia oryzae and areactive against Oomycetes such as, for example, Phythophtora andPlasmopara).

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weed-killers. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they are notwanted. Whether the substances according to the invention act as totalor selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, inlawns, turf and pasture-land, and for the selective combating of weedsin annual cultures.

The compounds of the formula (I) according to the invention are verysuitable for the selective pre-emergence combatting of monocotyledonweeds in dicotyledon cultures. They can be employed, for example, insoya bean with great success for the combatting of grass weeds.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable:

for example ammonium salts and ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates, as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifying and/or foamforming agents there are suitable: for examplenon-ionic and anionic emulsifiers, such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates aswell as albumen hydrolysis products; as dispersing agents there aresuitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in their formulations, can also be used as mixtures withknown herbicides, finished formulations or tank mixes being possible.

Possible components for the mixtures are known herbicides, for exampleanilides such as, for example, diflufenican and propanil; arylcarboxylicacids such as, for example, dichloropicolinic acid, dicamba andpicloram; aryloxyalkanoic acids such as, for example, 2,4-D, 2,4-DB,2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoicesters such as, for example, diclofop-methyl, fenoxaprop-ethyl,fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones suchas, for example, chloridazon and norflurazon; carbamates such as, forexample, chlorpropham, desmedipham, phenmedipham and propham;chloroacetanilides such as, for example, alachlor, acetochlor,butachlor, metazachlor, metolachlor, pretilachlor and propachlor;dinitroanilines such as, for example, oryzalin, pendimethalin andtrifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox,fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureassuch as, for example, chlortoluron, diuron, fluometuron, isoproturon,linuron and methabenzthiazuron; hydroxylamines such as, for example,alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim;imidazolinones such as, for example, imazethapyr, imazamethabenz,imazapyr and imazaquin; nitriles such as, for example, bromoxynil,dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet;sulfonylureas such as, for example, amidosulfuron, bensulfuron-methyl,chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl,nicosulfuron, primisulfuron, pyrazosulfuron-ethyl thifensulfuron-methyl,triasulfuron and tribenuron-methyl; thiolcarbamates such as, forexample, butylate, cycloate, di-allate, EPTC, esprocarb, molinate,prosulfocarb, thiobencarb and tri-allate; triazines such as, forexample, atrazine, cyanazine, simazine, simetryn, terbutryn andterbutylazine; triazinones such as, for example, hexazinone, metamitronand metribuzin; others such as, for example, aminotriazole, benfuresate,bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr,ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben,pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellants, plant nutrientsand agents which improve soil structure, are also possible.

The insecticides include, for example, phosphates, carbamates,carboxylic esters, chlorinated hydrocarbons, phenolic ureas, substancesproduced by microorganisms, and others. The following compounds may bementioned:

Acrinathrin, alphamethrin, betacyfluthrin, bifenthrin, brofenprox,cis-resmethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin,cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin,fenvalerate, flucythrinate, fluvalinate, lambda-cyhalothrin, permethrin,pyresmethrin, pyrethrum, silafluofen, tralomethrin zeta-methrin,alanycarb, bendiocarb, benfuracarb, bufencarb, butocarboxim carbaryl,cartap, ethiofencarb, fenobucarb, fenoxycarb, isoprocarb, methiocarb,methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, terbamthiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, acephate, azinphosA, azinphos M, bromophos A cadusafos, carbophenothion, chlorfenvinphos,chlormephos, chlorpyrifos, chlorpyrifos M, cyanophos, demeton M,demetons-methyl, demeton S, diazinon, dichlorvos, dicliphos,dichlorfenthion, dicrotophos, dimethoate, dimethylvinphos, dioxathion,disulfoton, edifenphos, ethion, etrimphos, fenitrothion, fenthion,fonophos, formothion, heptenophos, iprobenfos, isazophos, isoxathion,phorate, malathion, mecarbam, mervinphos, mesulfenphos, methacrifos,methamidophos, naled, omethoate, oxydemeton M, oxydeprofos, parathion A,parathion M, phenthoate, phorate, phosalone, phosmet, phosphamdom,phoxim, pirimiphos A, pirimiphos M, propaphos, prothiophos, prothoate,pyraclophos, pyridaphenthion, quinalphos, salithion, sebufos, sulfotep,sulprofos, tetrachlorvinphos, temephos, thiomethon, thionazin,trichlorfon, triazophos, vamidothion, buprofezin, chlorfluazuron,diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, pyriproxifen,tebufenozide, teflubenzuron, triflumoron, imidacloprid, nitenpyram N-(6-chloro-3-pyridinyi)methyl!-B'-cyano-N-methyl-ethanimideamide (NI-25),abamectin, amitrazin, avermectin, azadirachtin, bensultap, Bacillusthuringiensis, cyromazine, diafenthiuron, emamectin, ethofenprox,fenpyrad, fipronil, flufenprox, lufenuron, metaldehyde, milbemectin,pymetrozine, tebufenpyrad, triazuron, aldicarb, bendiocarb, benfuracarb,carbofuran, carbosulfan, chlorethoxyfos, cloethocarb, disulfoton,ethophrophos, etrimphos, fenamiphos, fipronil, fonofos, fosthiazate,furathiocarb, HCH, isazophos, isofenphos, methiocarb, monocrotophos,nitenpyram, oxamyl, phorate, phoxim, prothiofos, pyrachlofos, sebufos,silafluofen, tebupirimphos, tefluthrin, terbufos, thiodicarb, thiafenox,azocyclotin, butylpyridaben, clofentezine, cyhexatin, diafenthiuron,diethion, emamectin, fenzaquin, fenbutatin oxide, fenothiocarb,fenpropathrin, fenpyrad, fenpyroximate, fluazinam, fluazuron,flucycloxuron, flufenoxuron, fluvalinate, fubfenprox, hexythiazox,ivemectin, methidathion, monocrotophos, moxidectin, naled, phosalone,profenofos, pyraclofos, pyridaben, pyrimidifen, tebufenpyrad,thuringiensin, triarathene and4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile(AC 303630).

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 10 g and 10 kg of active compound perhectare of soil surface, preferably between 50 g and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example Ia-1 ##STR27##

1.47 g (15.5 mmol) of chloromethyl ethyl ether in 15 ml of absolutedichloromethane are added dropwise under a nitrogen atmosphere from 0°C. to 10° C. to 4.3 g (15 mmol) of3-(2,4,6-trimethylphenyl)-4-hydroxy-5,5-pentamethylene-Δ³-dihydrofuran-2-one in 60 ml of absolute dichloromethane, 1.67 g (16.5mmol) of triethylamine and a spatula tip of DMAP. The reaction mixtureis stirred at room temperature for about 20 hours, then washed insuccession with 10% strength citric acid, sodium hydrogen carbonatesolution and sodium chloride solution, the organic phase is dried oversodium sulphate, and the solvent is stripped off. The crude product ispurified further on a silica gel column (eluent:chloroform/ethyl acetate3:1).

2.47 g (53% of theory) are obtained of3-(2,4,6-trimethylphenyl)-4-ethoxymethyloxy)-5,5-pentamethylene-Δ.sup.3-dihydrofuran-2-one, of melting point m.p. 102° C.

In analogy to Example I, the compound of the following preparationexamples of the formula (Ita) were synthesized ##STR28##

                                      TABLE 1                                     __________________________________________________________________________    Ex.                                           Physical                        No A  B         L    X  Y  Z.sub.n                                                                           M              constants                       __________________________________________________________________________    Ia-2                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                                       oil                             Ia-3                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H                                                                                  ##STR29##     m.p.: 106° C.            Ia-4                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   OC.sub.2 H.sub.5                                                                             m.p.: 67° C.             Ia-5                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   OC.sub.8 H.sub.17 -n                                                                         m.p.: 62° C.             Ia-6                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H                                                                                  ##STR30##     m.p.: 57° C.             Ia-7                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   OCOC.sub.4 H.sub.9 -t                                                                        m.p.: 96° C.             Ia-8                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   OC.sub.2 H.sub.4 OCH.sub.3                                                                   m.p.: 67° C.             Ia-9                                                                             (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        OC.sub.3 H.sub.7 -i                                                                          m.p.: 81-82° C.          Ia-10                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        OCOC.sub.4 H.sub.9 -t                                                                        m.p.: 98-99° C.          Ia-11                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        OC.sub.4 H.sub.9 -i                                                                          oil                             Ia-12                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR31##     oil                             Ia-13                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR32##     oil                             Ia-14                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR33##     oil                             Ia-15                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR34##     oil                             Ia-16                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H                                                                                  ##STR35##     m.p.: 65° C.             Ia-17                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   SCH.sub.3      m.p.: 120° C.            Ia-18                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   CN             m.p.: 158° C.            Ia-19                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   COC.sub.4 H.sub.9 -t                                                                         m.p.: 128° C.            Ia-20                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   COOCH.sub.3    m.p.: 127° C.            Ia-21                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl Cl H   COOC.sub.4 H.sub.9 -t                                                                        M.P.: 126° C.            Ia-22                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           Cl H  6-F CN             m.p.: 163° C.            Ia-23                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        OCH.sub.2 C CH m.p.: 243° C.            Ia-24                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR36##     m.p.: 172-173° C.        Ia-25                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR37##     m.p.: 145° C.-146        Ia-26                                                                             ##STR38##   CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        OC.sub.2 H.sub.5                                                                             oil                             Ia-27                                                                             ##STR39##   CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR40##     oil                             Ia-28                                                                             ##STR41##   CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR42##     m.p.: 145-147° C.        Ia-29                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        SCH.sub.3      m.p.: 125-127° C.        Ia-30                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR43##     m.p.: 156-157° C.        Ia-31                                                                             ##STR44##   CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                         ##STR45##     oil                             Ia-32                                                                            (CH.sub.2).sub.5                                                                           CH.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         6-CH.sub.3                                                                        CHCH.sub.2     m.p.: 89-91°             __________________________________________________________________________                                                  C.                          

In analogy to Example Ia-1, the Preparation Example Ib-1 is alsoobtained:

¹ H-NMR (200 1MHz, CDCl₃): 2.12, 2.2, 2.26 (3s, 9H, Ar-CH₃), 3.88 (s,3H, SO₂, CH₃), 3.92 (s, 3H, N-CH₃), 3.25, 3.62 (m, 2H, N-CH₂), 4.21 (dd,1H, CH-N) 4,72 (ABq, 2H, O-CH₂ N), 6.89 (s, 2H, Ar-H). ##STR46##

In analogy to Example Ia-1, the preparation example of formula (Ic-1) isalso obtained, melting point m.p. 207° C.

Example Ic-1 ##STR47## USE EXAMPLES

In the following use examples, the compound listed below was employed ascomparison substance: ##STR48##4-Methoxy-3-(3-trifluoromethylphenyl)-5-methyl-5H-furan-2-one (knownfrom DE 39 31 773, Example 6).

Example A

Panonychus test

    ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted withemulsifier containing water to the desired concentration.

About 30 cm high plum trees (Prunus domestica) which are heavilyinfested with all development stages of the fruit tree red spider mite(Panonychus ulmi) are sprayed with a preparation of the active compoundof the desired concentration.

After the desired time, the action in % is determined. 100% means thatall the spider mites have been killed; 0% means that none of the spidermites have been killed.

In this test, for example, the compounds of Preparation Examples Ia-1,Ia-2, Ia-5 and Ia-7 at an active compound concentration, used by way ofexample, of 0.02% brought about a destruction of 100% after 7 days.

Example B

Tetranychus test (OP resistent)

    ______________________________________                                        Solvent:    3 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are infested with all developmentstages of the of the common or two-spotted spider mite (Tetranychusurticae) are treated by being dipped into the preparation of the activecompound of the desired concentration.

After the desired time, the destruction in % is determined. 100% meansthat all the spider mites have been killed; 0% means that none of thespider mites have been killed.

In this test, for example, the compounds of Preparation Examples Ia-1,Ia-2, Ia-5 and Ia-7 at an active compound concentration, used by way ofexample, of 0.02% brought about a destruction of at least 98% after 7days.

Example C

Pre-emergence test

    ______________________________________                                        Solvent:    5 parts by weight of acetone                                      Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the compounds according to PreparationExample (Ia-1) and (Ia-2) display a very strong action against weedswhile in some cases being very well tolerated by crop plants such as,for example, wheat and soya bean. At an application rate, used by way ofexample, of 1000 g/ha, Alopecurus, Cynodon, Digitaria, Lolium andSetaria for example, are at least 90% affected.

Example D

Phaedon larvae test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae) for as long asthe leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, for example, the compounds of Preparation Examples Ia-9,Ia-12, Ia-13 Ia-14, Ia-15, Ib-1 and Ic-1 at an active compoundconcentration, used by way of example, of 0.01% brought about adestruction of 100% after 7 days, whereas the known compound (A) broughtabout no destruction.

Example E

Plutella test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellamaculipennis) for as long as the leaves are still moist.

After the desired time, the destruction in % is determined. 100% meansthat all the caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example, the compounds of Preparation Examples Ia-14and Ia-27, at an active compound concentration, used by way of example,of 0.01% brought about a destruction of 100% after 3 days, whereas theknown compound (A) brought about no destruction.

Example F

Nephotettix test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza saliva) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with the rice green leafhopper (Nephotettix cincticeps) for aslong as the seedlings are still damp.

In this test, for example, the compounds of Preparation Examples Ia-1,Ia-3, Ia-9, Ia-12, Ia-13, Ia-15, Ia-25, Ia-26, Ia-27, Ia-28, Ia-31, Ib-1and Ic-1 at an active compound concentration, used by way of example, of0.01% brought about a destruction of 100% after 6 days, whereas theknown compound (A) brought about no destruction.

Example G

Myzus test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                            Emulsifier: 1 part by weight of alkylaryl polyglycol ether                    ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested with thepeach aphid are treated by being dipped into the preparation of activecompound of the desired concentration.

After the desired time, the action is determined. 100% means that allthe aphids have been killed; 0% means that none of the aphids have beenkilled.

In this test, for example, the compounds of Preparation Examples Ia-1,Ia-28 and Ia-31 at an active compound concentration, used by way ofexample, of 0.1% brought about a destruction of 100% after 6 days,whereas the known compound (A) brought about no destruction.

We claim:
 1. A substituted aryl keto-enolic heterocycle of the formula##STR49## in which X represents alkyl, halogen or alkoxy,Y representshydrogen, alkyl, halogen, alkoxy or halogenoalkyl, Z represents alkyl,halogen or alkoxy, n represents a number 0, 1, 2 or 3, Het represents aheterocyclic group selected from the group consisting of ##STR50## A andB can be identical or different and represent hydrogen, in each caseoptionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,alkylthioalkyl, cycloalkyl which is optionally interrupted by at leastone heteroatom, or aryl, aralkyl or hetaryl each of which is optionallysubstituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy ornitro, A and B, together with the carbon atom to which they areattached, form a saturated or unsaturated ring which is optionallyinterrupted by at least one heteroatom and is optionally substituted, Erepresents hydrogen, in each case optionally halogen-substituted alkyl,alkenyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl which is optionallyinterrupted by at least one heteroatom, or aryl, aralkyl or hetaryl eachof which is optionally substituted by halogen, alkyl, halogenoalkyl,alkoxy, halogenoalkoxy or nitro, or in which A and E, together with theatoms to which they are attached, form a saturated or unsaturatedmonocyclic, bicyclic or tricyclic ring system which is optionallyinterrupted by at least one heteroatom and is optionally substituted, Lrepresents an alkanediyl group, M represents one of the followinggroups: ##STR51## in which R¹ represents hydrogen or alkyl,R² representsin each case optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl,alkoxyalkyl, alkylthioalkyl, aryl or aralkyl, R³ represents optionallysubstituted alkyl, aryl or aralkyl, or the enantiomerically pure formsthereof.
 2. A compound according to claim 1, in whichX represents C₁ -C₆-alkyl, halogen or C₁ -C₆ -alkoxy, Y represents hydrogen, C₁ -C₆ -alkyl,halogen C₁ -C₆ -alkoxy or C₁ -C₃ -halogenoalkyl, Z represents C₁ -C₆-alkyl, halogen or C₁ -C₆ -alkoxy, n represents a number from 0 to 3,Het represents a heterocyclic group selected from the group consistingof ##STR52## in which A and B are identical or different and representhydrogen or in each case optionally halogen-substituted straight-chainor branched C₁ -C₁₂ -alkyl, C₃ -C₈ -alkenyl, C₁ -C₁₀ -alkoxy-C₂ -C₈-alkyl, C₁ -C₈ -polyalkoxy-C₂ -C₈ -alkyl, C₁ -C₁₀ -alkylthio-C₂ -C₈-alkyl, cycloalkyl having 3 to 8 ring atoms, which can be interrupted byoxygen and/or sulphur, or phenyl, pyrimidyl, imidazolyl, pyrazolyl,triazolyl, indolyl, thiazolyl or phenyl-C₁ -C₆ -alkyl each of which isoptionally substituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁-C₆ -alkoxy, C₁ -C₆ -halogenoalkoxy or nitro, or in which A and B,together with the carbon atom to which they are attached, form asaturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byhalogen, C₁ -C₆ -alkyl, C₁ -C₆ alkoxy, C₁ -C₄ -halogenoalkyl, C₁ -C₄-halogenoalkoxy, C₁ -C₄ -alkylthio or phenyl which is optionallysubstituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, E representshydrogen or in each case optionally halogen-substituted straight-chainor branched C₁ -C₁₂ -alkyl, C₃ -C₈ -alkenyl, C₁ -C₁₀ -alkoxy-C₂ -C₈-alkyl, C₁ -C₈ -polyalkoxy-C₂ -C₈ -alkyl, C₁ -C₁₀ -alkylthio-C₂ -C₈-alkyl, cycloalkyl having 3 to 8 ring atoms, which can be interrupted byoxygen and/or sulphur, or phenyl, pyrimidyl, imidazolyl, pyrazolyl,triazolyl, indolyl, thiazolyl or phenyl-C₁ -C₆ -alkyl each of which isoptionally substituted by halogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₁-C₆ -alkoxy, C₁ -C₆ -halogenoalkoxy or nitro, or in which A and E,together with the atoms to which they are attached, form a saturated orunsaturated 3- to 8-membered ring which is optionally interrupted byoxygen and/or sulphur and is optionally substituted by halogen, C₁ -C₆-alkyl, C₁ -C₆ alkoxy, C₁ -C₄ -halogenoalkyl, C₁ -C₄ -halogenoalkoxy, C₁-C₄ -alkylthio or phenyl which is optionally substituted by halogen, C₁-C₆ -alkyl, C₁ -C₆ -alkoxy, or, if Het in formula (I) represents apyrazolinone ring, A and E, together with two nitrogen atoms of thepyrazoline ring, represent a group of the formulae 1 to 4 listed below##STR53## which is optionally monosubstituted or polysubstituted byidentical or different substituents consisting of C₁ -C₆ -alkyl, C₁ -C₆-halogenoalkyl or halogen, L represents an alkanediyl group having 1 to6 carbon atoms, M represents one of the following: ##STR54## R¹represents hydrogen or C₁ -C₁₂ -alkyl, R² represents in each caseoptionally halogen-substituted C₁ -C₁₂ -alkyl, C₃ -C₈ -alkenyl, C₃ -C₈-alkinyl, C₃ -C₈ -cycloalkyl, C₁ -C₈ -alkoxy-C₂ -C₈ -alkyl, C₁ -C₈-alkylthio-C₂ -C₈ -alkyl or phenyl or benzyl each of which is optionallysubstituted by halogen, nitro, cyano, C₁ -C₆ -alkoxy, C₁ -C₆-haloalkylthio, C₁ -C₆ -alkyl or C₁ -C₆ -halogenoalkyl, R³ representsoptionally halogen-substituted C₁ -C₁₂ -alkyl, or represents phenyl orbenzyl each of which is substituted by halogen, C₁ -C₆ -alkyl or C₁ -C₆-alkoxy, or the enantiomerically pure forms thereof.
 3. A compoundaccording to claim 1, in whichX represents C₁ -C₆ -alkyl, fluorine,chlorine, bromine or C₁ -C₆ -alkoxy, Y represents hydrogen, C₁ -C₆-alkyl, fluorine, chlorine, bromine, C₁ -C₆ -alkoxy or C₁ -C₂-halogenoalkyl, Z represents C₁ -C₄ -alkyl, fluorine, chlorine, bromineor C₁ -C₄ -alkoxy, n represents a number from 0 to 2, Het represents aheterocyclic group selected from the group consisting of ##STR55## inwhich A and B are identical or different and represent hydrogen, in eachcase optionally halogen-substituted straight-chain or branched C₁ -C₁₀-alkyl, C₃ -C₆ -alkenyl, C₁ -C₈ -alkoxy-C₂ -C₆ -alkyl, C₁ -C₆-polyalkoxy-C₂ -C₆ -alkyl, C₁ -C₈ -alkylthio-C₂ -C₆ -alkyl, cycloalkylhaving 3 to 7 ring atoms, which can be interrupted by 1-2 oxygen and/orsulphur atoms, or phenyl, pyridinyl, imidazolyl, pyrazolyl, triazolyl,indolyl, thiazolyl or phenyl-C₁ -C₄ -alkyl each of which is optionallysubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄-alkoxy, or nitro, or in which A and B, together with the carbon atom towhich they are attached, form a saturated or unsaturated 3- to8-membered ring which is optionally interrupted by oxygen and/or sulphurand is optionally substituted by halogen, C₁ -C₅ -alkyl, C₁ -C₅ alkoxy,C₁ -C₃ -halogenoalkyl, C₁ -C₄ -halogenoalkoxy, C₁ -C₃ -alkylthio orphenyl which is optionally substituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, E represents hydrogen or in each case optionallyhalogen-substituted straight-chain or branched C₁ -C₁₀ -alkyl, C₃ -C₆-alkenyl, C₁ C₈ -alkoxy-C₂ -C₆ -alkyl, C₁ -C₆ -polyalkoxy-C₂ -C₆ -alkyl,C₁ -C₈ -alkylthio-C₂ -C₆ -alkyl, cycloalkyl having 3 to 7 ring atoms,which can be interrupted by 1-2 oxygen and/or sulphur atoms, or phenyl,pyridinyl, imidazolyl, pyrazolyl, triazolyl, indolyl, thiazolyl orphenyl-C₁ -C₄ -alkyl each of which is optionally substituted by halogen,C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₄ -alkoxy or nitro, or inwhich A and E, together with the atoms to which they are attached, forma saturated or unsaturated 3- to 8-membered ring which is optionallyinterrupted by oxygen and/or sulphur and is optionally substituted byhalogen, C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, C₁ -C₃ -halogenoalkyl, C₁ -C₄ -halogenoalkoxy, C₁ -C₃ -alkylthio or phenyl which is optionallysubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, or, if Het informula (I) represents a pyrazolinone ring, A and E, together with thetwo nitrogen atoms of the pyrazoline ring, represent a group of theformulae 1 or 2 listed below which is optionally monosubstituted orpolysubstituted by identical or different substituents consisting of C₁-C₄ -alkyl, C₁ -C₄ -halogenoalkyl, fluorine or chlorine, ##STR56## Lrepresents an alkanediyl group having 1 to 4 carbon atoms, M representsone of the following groups: ##STR57## R¹ represents hydrogen or C₁ -C₁₀-alkyl, R² represents in each case optionally fluorine-, chlorine-,bromine-substituted C₁ -C₁₀ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₃-C₈ -cycloalkyl, C₁ -C₆ -alkoxy-C₂ -C₆ -alkyl, C₁ -C₆ -alkylthio-C₂ -C₆-alkyl, or phenyl or benzyl each of which is optionally substituted byfluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkylthio, C₁ -C₄-alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -halogenoalkylthio, C₁ -C₄ alkylor C₁ -C₄ -halogenoalkyl, R³ represents optionally fluorine-, chlorine-,bromine-substituted C₁ -C₁₀ -alkyl, or represents phenyl or benzyl eachof which is substituted by fluorine, chlorine, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, or the enantiomerically pure form thereof.
 4. A compoundaccording to claim 1, in whichX represents methyl, ethyl, propyl,isopropyl, fluorine, chlorine, bromine or methoxy, Y representshydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,fluorine, chlorine, bromine, methoxy, ethoxy and trifluoromethyl, Zrepresents methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert-butyl, fluorine, chlorine, bromine, methoxy and ethoxy, nrepresents 1, Het represents a heterocyclic group selected from thegroup consisting of ##STR58## in which A and B are identical ordifferent and represent hydrogen, in each case optionally fluorine- orchlorine-substituted straight-chain or branched C₁ -C₈ -alkyl, C₃ -C₄-alkenyl, C₁ -C₆ -alkoxy-C₂ -C₄ -alkyl, C₁ -C₄ -polyalkoxy-C₂ -C₄-alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, cycloalkyl having 3 to 6 ringatoms, which can be interrupted by 1-2 oxygen and/or sulphur atoms, orphenyl, pyridinyl, imidazolyl, indolyl or phenyl-C₁ -C₃ -alkyl each ofwhich is optionally substituted by fluorine, chlorine, methyl, ethyl,propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro, or inwhich A and B, together with the carbon atom to which they are attached,form a saturated or unsaturated 3- to 8-membered ring which isoptionally interrupted by oxygen and/or sulphur and is optionallysubstituted by fluorine, chlorine, C₁ -C₄ -alkyl, C₁ -C₄ alkoxy,trifluoromethyl, C₁ -C₂ -alkylthio or phenyl which is optionallysubstituted by fluorine, chlorine, methyl, methoxy, E representshydrogen or in each case optionally fluorine- or chlorine-substitutedstraight-chain or branched C₁ -C₈ -alkyl, C₃ -C₄ -alkenyl, C₁ -C₆-alkoxy-C₂ -C₄ -alkyl, C₁ -C₄ -polyalkoxy-C₂ -C₄ -alkyl, C₁ -C₆-alkylthio-C₂ -C₄ -alkyl, cycloalkyl having 3 to 6 ring atoms, which canbe interrupted by 1-2 oxygen and/or sulphur atoms, or represents phenyl,pyridinyl, imidazolyl, indolyl or phenyl-C₁ -C₃ -alkyl which isoptionally substituted by fluorine, chlorine, methyl, ethyl, propyl,isopropyl, methoxy, ethoxy, trifluoromethyl or nitro, or in which A andE, together with the atoms to which they are attached, form a saturatedor unsaturated 3- to 8-membered ring which is optionally interrupted byoxygen and/or sulphur and is optionally substituted by fluorine,chlorine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl, C₁ -C₂-alkylthio or phenyl which is optionally substituted by fluorine,chlorine, methyl, methoxy, or, if Het in formula (I) represents apyrazolinone ring, A and E, together with the two nitrogen atoms of thepyrazoline ring, represent a group of the formulae 1 or 2 listed belowwhich is optionally monosubstituted to trisubstituted by identical ordifferent substituents consisting of methyl, fluorine or chlorine,##STR59## L represents one of the following groups, ##STR60## Mrepresents one of the following groups: ##STR61## R¹ represents hydrogenor C₁ -C₈ -alkyl, R² represents in each case optionally fluorine-,chlorine-, bromine-substituted C₁ -C₈ -alkyl, C₃ -C₄ -alkenyl, C₃ -C₄-alkinyl, cyclopropyl, cyclopentyl, cyclohexyl, C₁ -C₆ -alkoxy-C₂ -C₄-alkyl, C₁ -C₆ -alkylthio-C₂ -C₄ -alkyl, or represents phenyl or benzyleach of which is optionally substituted by fluorine, chlorine, bromine,nitro, cyano, methylthio, ethylthio, methoxy, ethoxy,trifluoromethylthio, trifluoromethoxy, methyl, ethyl, trifluoromethyl,or the enantiomerically pure form thereof.
 5. A process for thepreparation of the substituted aryl keto-enolic heterocycle according toclaim 1, wherein in order to obtain a compound of the formula (la),##STR62## in which A, B, L, M, X, Y, Z and n have the meaning given inclaim 11, a compound of the formula (IIa) ##STR63## in which A, B, X, Y,Z and n have the meaning given in claim 11 is reacted with compounds ofthe formula (III)

    G--L--M                                                    (III)

in which L and M have the meaning given in claim 11 and G represents aleaving group, in the presence of a diluent and in the presence of abase; (B) in order to obtain compounds of the formula (Ib) ##STR64## inwhich A, B, E, L, M, X, Y, Z and n have the meaning in claim 11 acompound of the formula (IIb) ##STR65## in which A, B, E, X, Y, Z and nhave the meaning in, claim 11 is reacted with compounds of the formula(III)

    G--L--M                                                    (III)

in which L and M have the meaning given above and G represents a leavinggroup in the presence of a diluent and in the presence of a base; and(C) in order to obtain a compound of the formula (Ic) ##STR66## in whichA, E, L, M, X, Y, Z and n have the meaning given in claim 1 a compoundof the formula (IIc) ##STR67## in which B, E, X, Y, Z and n have themeaning given in claim 1 is reacted with a compound of the formula (III)

    G--L--M                                                    (III)

in which L and M have the meaning given above and G represents a leavinggroup in the presence of a diluent and in the presence of a base.
 6. Acompound according to claim 1, wherein Het is ##STR68##
 7. A compoundaccording to claim 1, wherein Het is ##STR69##
 8. A compound accordingto claim 1, wherein Het is ##STR70##
 9. A pesticidal or herbicidalcomposition which comprises a peticidally or herbicidally effectiveamount of a compound according to claim 1 and an inert carrier.
 10. Amethod of combatting pests in plant protection, the household sector andin the protection of stored products which comprises apply to said pestsor to a habitate to which they reside an effective amount of a compoundaccording to claim
 1. 11. The method according to claim 8 wherein thepest is an arthropod or a phytopantogenic fungi.
 12. A method ofcombatting unwanted plant growth which comprises applying to theunwanted plant or to an environment where it resides, an effectiveamount of a compound according to claim
 1. 13. A process for preparing apesticidal composition which comprises mixing a compound according toclaim 1 with an extender or a surface-active agent.